Electrocatalytic and photocatalytic performance of noble metal doped monolayer MoS2 in the hydrogen evolution reaction: A first principles study

To maximize the catalytic performance of MoS_(2) in the hydrogen evolution reaction,we investigate the electrocatalytic and photocatalytic performance of monolayer MoS_(2) doped with noble metal(Ag,Au,Cu,Pd,and Pt)using first principles calculation combined with the climbing image nudged elastic band method.We find the band gap of the monolayer MoS_(2) is reduced significantly by the noble metal doping,which is unfavorable to improving its photocatalytic performance.The optical absorption coefficient shows that the doping does not increase the ability of the monolayer MoS_(2) to absorb visible light.The monolayer MoS_(2) doped with the noble metal is not a potential photocatalyst for the hydrogen evolution reaction because the band edge position of the conduction band minimum is lower than-4.44 eV,the reduction potential of H^(+)/H_(2).Fortunately,the band gap reduction increases the electron transport performance of the monolayer MoS_(2),and the activation energy of water splitting is greatly reduced by the noble metal doping,especially the Pt doping.On the whole,noble metal doping can enhance the electrocatalytic performance of the monolayer MoS_(2).

Phonon Confinement Effect in Two-dimensional Nanocrystallites of Monolayer MoS_2 to Probe Phonon Dispersion Trends Away from Brillouin-Zone Center

The fundamental momentum conservation requirement q - 0 for the Raman process is relaxed in the nanocrystal- lites （NCs）, and phonons away from the Brillouin-zone center will be involved in the Raman scattering, which is well-known as the phonon confinement effect in NCs. This usually gives a downshift and asymmetric broadening of the Raman peak in various NCs. Recently, the A1 mode of 1L MoS2 NCs is found to exhibit a blue shift and asymmetric broadening toward the high-frequency side [Chem. Soc. Rev. 44 （2015） 2757 and Phys. Rev. B 91 （2015） 195411]. In this work, we carefully check this issue by studying Raman spectra of lL MoS2 NCs prepared by the ion implantation technique in a wide range of ion-implanted dosage. The same confinement coefficient is used for both E＇ and A＇1 modes in 1L MoS2 NCs since the phonon uncertainty in an NC is mainly determined by its domain size. The asymmetrical broadening near the A＇1 and E＇ modes is attributed to the appearance of defect-activated phonons at the zone edge and the intrinsic asymmetrical broadening of the two modes, where the anisotropy of phonon dispersion curves along Г-K and Г- M is also considered. The photoluminescence spectra confirm the formation of small domain size of 1L MoS2 nanocrystallites in the ion-implanted 1L MoS2. This study provides not only an approach to quickly probe phonon dispersion trends of 2D materials away from Г by the Raman scattering of the corresponding NCs, but also a reference to completely understand the confinement effect of different modes in various nanomaterials.

Raman Scattering Modification in Monolayer ReS_2 Controlled by Strain Engineering

Regulation of optical properties and electronic structure of two-dimensionM layered ReS2 materials has attracted much attention due to their potential in electronic devices. However, the identification of structure transformation of monolayer ReS2 induced by strain is greatly lacking. In this work, the Raman spectra of monolayer ReS2 with external strain are determined theoretically based on the density function theory. Due to the lower structural symmetry, deformation induced by external strain can only regulate the Raman mode intensity but cannot lead to Raman mode shifts. Our calculations suggest that structural deformation induced by external strain can be identified by Raman scattering.

Poisoning of MoO_3 Precursor on Monolayer MoS_2 Nanosheets Growth by Tellurium-Assisted Chemical Vapor Deposition

We obtain molybdenum disulfide （MoS2） nanosheets （NSs） with edge sizes of 18μm by direct sulfuration of MoO3 powder spread on the SiO2/Si substrates. However, the undesirable MoO3 nanoparticles （NPs） left on the surface of MoS22 NSs poison the MoO3 precursor. Introducing Te vapors to react with MoS2 to form low melting point intermediate MoSxTe2-x, the evaporations of MoO3 precursor recover and MoO3 NPs disappear. Thus Te vapor is effective to suppress poisoning of the MoO3 precursor. Selecting the appropriate amount of Te vapor, we fabricate monolayer MoS22 NSs up to 70μm in edge length. This finding can be significant to understand the role of Te in the Te-assisted chemical vapor deposition growth process of layered chalcogenide materials.

Enhanced Performance of a Monolayer MoS_2/WSe_2 Heterojunction as a Photoelectrochemical Cathode

Transition-metal dichalcogenide(TMD) semiconductors have attracted interest as photoelectrochemical(PEC) electrodes due to their novel band-gap structures,optoelectronic properties, and photocatalytic activities.However, the photo-harvesting efficiency still requires improvement. In this study, A TMD stacked heterojunction structure was adopted to further enhance the performance of the PEC cathode. A P-type WSe_2 and an N-type Mo S_2 monolayer were stacked layer-by-layer to build a ultrathin vertical heterojunction using a micro-fabrication method.In situ measurement was employed to characterize the intrinsic PEC performance on a single-sheet heterostructure.Benefitting from its built-in electric field and type II band alignment, the MoS_2/WSe_2 bilayer heterojunction exhibited exceptional photocatalytic activity and a high incident photo-to-current conversion efficiency(IPCE). Comparing with the monolayer WSe_2 cathode, the PEC current and the IPCE of the bilayer heterojunction increased by a factor of 5.6 and enhanced 50%, respectively. The intriguing performance renders the MoS_2/WSe_2 heterojunction attractive for application in high-performance PEC water splitting.

Investigation of Single-Wall MoS_2 Monolayer Flakes Grown by Chemical Vapor Deposition

Recently, two-dimensional monolayer molybdenum disulfide(MoS_2), a transition metal dichalcogenide, has received considerable attention due to its direct bandgap, which does not exist in its bulk form, enabling applications in optoelectronics and also thanks to its enhanced catalytic activity which allows it to be used for energy harvesting. However,growth of controllable and high-quality monolayers is still a matter of research and the parameters determining growth mechanism are not completely clear. In this work, chemical vapor deposition is utilized to grow monolayer MoS_2 flakes while deposition duration and temperature effect have been systematically varied to develop a better understanding of the MoS_2 film formation and the influence of these parameters on the quality of the monolayer flakes. Different from previous studies, SEM results show that single-layer MoS_2 flakes do not necessarily grow flat on the surface, but rather they can stay erect and inclined at different angles on the surface, indicating possible gas-phase reactions allowing for monolayer film formation. We have also revealed that process duration influences the amount of MoO_3/MoO_2 within the film network. The homogeneity and the number of layers depend on the change in the desorption–adsorption of radicals together with sulfurization rates, and, inasmuch, a careful optimization of parameters is crucial. Therefore, distinct from the general trend of MoS_2 monolayer formation, our films are rough and heterogeneous with monolayer MoS_2 nanowalls. Despite this roughness and the heterogeneity, we observe a strong photoluminescence located around 675 nm.

Transport through a Single Barrier on Monolayer MoS2

We investigate theoretically quantum transport through a single barrier on monolayer MoS2. It is found that the transmission properties of spin-up （down） electrons in the K valley are the same as spin-down （up） electrons in the K＇ valley due to the time-reversal symmetry. Generally, the transmission probability for transport through an n-n-n （or p p-p） junction is an oscillating function of incident angle, barrier height, as well as the incident energy of electrons. The present transmission shows a directional-dependent tunneling depending sensitively on the spin orientation for transport through a p-p p junction. While for transport through an n-p-n junction, monolayers of MoS2 become opaque for almost all angles of incident Oo except for θ0-θ0m （the resonant angles）. The positions and numbers of resonant peaks in the transmission are determined by the distance between the two barriers and the spin orientation. The conductance in such systems can be tuned significantly by changing the height of the electric potential.

Interlayer coupling in anisotropic/isotropic van der Waals heterostructures of ReS2 and MoS2 monolayers

In-plane symmetry is an important contributor to the physical properties of two-dimensional layered materials, as well as atomically thin heterojunctions. Here, we demonstrate anisotropic/isotropic van der Waals （vdW） heterostructures of ReS2 and MoS2 monolayers, where interlayer coupling interactions and charge separation were observed by in situ Raman-photoluminescence spectroscopy, electrical, and photoelectrical measurements. We believe that these results could be helpful for understanding the fundamental physics of atomically thin vdW heterostructures and creating novel electronic and optoelectronic devices.

Thermal Evaporation Deposition of Few-layer MoS_2 Films

We present a study of the fabrication of monolayer MoS_2 on n-Si(111) substrates by modified thermal evaporation deposition and the optoelectrical properties of the resulting film. The as-grown MoS_2 ultrathin film is about 10 nm thick, or about a few atomic layers of MoS_2. The film has a large optical absorption range of 300-700 nm and strong luminescence emission at 682 nm. The optical absorption range covered almost the entire ultraviolet to visible light range, which is very useful for making high-efficiency solar cells. Moreover, the MoS_2/Si heterojunction exhibited good rectification characteristics and excellent photovoltaic effects. The power conversion efficiency of the heterojunction device is about 1.79% under white light illumination of 10 m W/cm^2. The results show that the monolayer MoS_2 film will find many applications in high-efficiency optoelectronic devices.

多巴胺在2-氨基-5-巯基-[1,3,4]三氮唑自组装膜电极上的准可逆行为研究及分析应用

利用新合成的巯基试剂2-氨基-5-巯基-[1,3,4]三氮唑在金电极表面进行了首次自组装,用电化学法和扫描电子显微镜对自组装膜电极进行了表征。研究了多巴胺在该自组装膜电极上的电化学行为,发现该自组装膜能有效促进多巴胺在电极与溶液之间的电子传递,表现为二电子传递的准可逆行为,电极反应速率常数为0.105cm/s。该自组装膜电极用于多巴胺注射液含量的测定,结果满意。

Ag nanowire/nanoparticle-decorated MoS2 monolayers for surface-enhanced Raman scattering applications

Developing well-defined nanostructures with superior surface-enhanced Raman scattering （SERS） performance is a critical and highly desirable goal for the practical applications of SERS in sensing and analysis. Here, a SERS-active substrate was fabricated by decorating a MoS2 monolayer with Ag nanowire （NW） and nanoparticle （NP） structures, using a spin-coating method. Both experimental and theoretical results indicate that strong SERS signals of rhodamine 6G （R6G） molecules can be achieved at ＂hotspots＂ formed in the Ag NW-Ag NP-MoS2 hybrid structure, with an enhancement factor of 106. The SERS enhancement is found to be strongly polarization dependent. The fabricated SERS substrate also exhibits ultrasensitive detection capabilities with a detection limit of 10-11 M, as well as reliable reproducibility and good stability.

New selection rule of resonant Raman scattering in MoS_(2) monolayer under circular polarization

The first-order resonant Raman spectra of monolayer MoS_(2)are calculated under the circularly polarized photoexcitation.The anomalously nonzero Raman intensity of the in-plane E mode under the Z(σ+σ+)Zor Z(σ−σ−)Zgeometry,which goes against the conventional selection rule,appears under some circum-stances when optical absorption occurs at some special reciprocal points between the zone-center Γ and the zone-edge-center M points.At that moment,the valley selectivity to the circular polarization is lifted.The analysis shows that the anomalous Raman intensity of the E mode for the same circularly polarized incident and scattered light is consistent with the pseudo-angular-momentum conservation law.The cal-culated E Raman tensor of monolayer MoS_(2)is found to vary with laser energy.The two diagonal terms of the Raman tensor change their signs from mutually opposite to the same when the relative intensity of the in-plane E mode to the out-of-plane A'_(1)mode increases,indicating the increasingly important role played by the Frölich-type electron-phonon interaction over the deformation potential.Our study may shed new light on the understanding of the novel electron-photon process and assist in the design of new type of optoelectronic devices.

Vertically coupled ZnO nanorods on MoS2 monolayers with enhanced Raman and photoluminescence emission

Hybrid structures composed of layered materials have received much attention due to their exceptional tunable optical, electronic and catalytic properties. Here, we describe a hydrothermal strategy for coupling vertical ZnO nanorods on MoS2 monolayers without a catalyst. These vapor-solid-grown MoS2 monolayers aid in growing vertical ZnO nanorods via epitaxy. Enhanced Raman and photoluminescence emissions were observed from the MoS2 monolayers under the ZnO nanorods in these coupled structures, which was attributed to the light antenna effect of the ZnO nanorods. These hybrid and incorporation protocols for layered materials will provide new perspectives and opportunities for promoting the construction of heterojunctions with adjustable layered structures leading to fascinating fundamental phenomena and advanced devices.

Influence of the velocity barrier on the massive Dirac electron transport in a monolayer MoS2 quantum structure

Using the transfer matrix method,spin-and valley-dependent electron transport properties modulated by the velocity barrier were studied in the normal/ferromagnetic/normal monolayer MoS2 quantum structure.Based on Snell’s Law in optics,we define the velocity barrier asξ=v2/v1 by changing the Fermi velocity of the intermediate ferromagnetic region to obtain a deflection condition during the electron transport process in the structure.The results show that both the magnitude and the direction of spin-and valley-dependent electron polarization can be regulated by the velocity barrier.−100%polarization of spin-and valley-dependent electron can be achieved forξ>1,while 100%polarization can be obtained forξ<1.Furthermore,it is determined that perfect spin and valley transport always occur at a large incident angle.In addition,the spin-and valley-dependent electron transport considerably depends on the length kFL and the gate voltage U(x)of the intermediate ferromagnetic region.These findings provide an effective method for designing novel spin and valley electronic devices.

Controlled synthesis of high-quality crystals of monolayer MoS_2 for nanoelectronic device application

Two-dimensional layered materials have attracted significant interest for their potential applications in electronic and optoelectronics devices. Among them, transition metal dichalcogenides(TMDs), especially molybdenum disulfide(MoS_2), is extensively studied because of its unique properties. Monolayer MoS_2 so far can be obtained by mechanical exfoliation or chemical vapor deposition(CVD). However, controllable synthesis of large area monolayer MoS_2 with high quality needs to be improved and their growth mechanism requires more studies. Here we report a systematical study on controlled synthesis of high-quality monolayer MoS_2 single crystals using low pressure CVD. Large-size monolayer MoS_2 triangles with an edge length up to 405 μm were successfully synthesized. The Raman and photoluminescence spectroscopy studies indicate high homogenous optical characteristic of the synthesized monolayer MoS_2 triangles. The transmission electron microscopy results demonstrate that monolayer MoS_2 triangles are single crystals. The back-gated field effect transistors(FETs) fabricated using the as-grown monolayer MoS_2 show typical n-type semiconductor behaviors with carrier mobility up to 21.8 cm^2 V^(-1) s^(-1), indicating excellent electronic property comparing with previously reported CVD grown MoS_2 monolayer. The MoS_2 FETs also show a high photoresponsivity of 7 A W^(-1), as well as a fast photo-response time of 20 ms. The improved synthesis method recommended here, which makes material preparation much easier, may strongly promote further research and potential applications.

Synthesis of MoX2 (X =Se or S) monolayers with high-concentration 1T'phase on 4H/fcc-Au nanorods for hydrogen evolution

Controlled synthesis of transition metal dichalcogenide (TMD) monolayers with unusual crystal phases has attracted increasing attention due to their promising applications in electrocatalysis.However,the facile and large-scale preparation of TMD monolayers with high-concentration unusual crystal phase still remains a challenge.Herein,we report the synthesis of MoX2 (X =Se or S) monolayers with high-concentration semimetallic 1T'phase by using the 4H/face-centered cubic (fcc)-Au nanorod as template to form the 4H/fcc-Au@MoX2 nanocomposite.The concentrations of 1T'phase in the prepared MoSe2 and MoS2 monolayers are up to 86% and 81%,respectively.As a proof-of-concept application,the obtained Au@MoS2 nanocomposite is used for the electrocatalytic hydrogen evolution reaction (HER) in acid medium,exhibiting excellent performance with a low overpotential of 178 mV at the current density of 10 mNcm^2,a small Tafel slope of 43.3 mV/dec,and excellent HER stability.This work paves a way for direct synthesis of TMD monolayers with high-concentration of unusual crystal phase for the electrocatalytic application.

Tip-enhanced photoluminescence spectroscopy of monolayer MoS_2

Probing the optical properties of molybdenum disulfide(MoS_2) is vital to its application in plasmon-enhanced spectroscopy, catalysts, sensing, and optoelectronic devices. In this paper, we theoretically studied the Raman and fluorescence properties of monolayer MoS_2 using tip-enhanced spectroscopy(TES). In the strong-coupling TES system, the Raman and fluorescence enhancement factors can be turned to as high as 4.5 × 10~8 and 3.3 × 10~3,respectively, by optimizing the tip–MoS_2-film distance. Our theoretical results not only help to deeply understand the TES properties of monolayer MoS_2, but also provide better guidance on the applications of the novel two-dimensional material.

Role of the carrier gas flow rate in monolayer MoS2 growth by modified chemical vapor deposition

Monolayer molybdenum disulfide （MoS2） has attracted much attention because of the variety of potential applications. However, its controlled growth is still a great challenge. Here, we report a modified chemical vapor deposition method to grow monolayer MoS2. We observed that the quality of the MoS2 crystals could be greatly improved by tuning the carrier gas flow rate during the heating stage. This subtle modification prevents the uncontrollable reaction between the precursors, a critical factor for the growth of high-quality monolayer MoS2. Based on an optimized gas flow rate, the MoS2 coverage and flake size can be controlled by adjusting the growth time.

Comparative adsorption of heavy metal ions in wastewater on monolayer molybdenum disulfide

To maximize the potential of monolayer molybdenum disulfide(MoS2)sheet in the disposal of heavy metal ions in wastewater,we compared the adsorption of several common heavy metal ions(including Cr^(3+),Ni^(2+),Cu^(2+),Zn^(2+),Cd^(2+),Hg^(2+),and Pb^(2+))in wastewater on the monolayer MoS2 sheet through first-principles calculation.Our simulation results show that the monolayer MoS2 sheet is a potential heavy metal adsorption material because of the attractive interaction between them.The most negative adsorption energy determines that the TMo site is the most stable adsorption site for the heavy metal ions.The attractive interaction is considered as chemical adsorption,and it is closely related to charge transfer.The orbital hybridization between S p and heavy metal ions p and d states electrons contributes to the adsorption,except the orbital hybridization between S p and Pb p states electrons contributes to the Pb^(2+) adsorption.All the results show that the monolayer MoS2 sheet is most suitable for removing Ni^(2+) and Cr^(3+) ions from wastewater,followed by Cu^(2+) and Pb^(2+).For the ions Cd^(2+),Zn^(2+),and Hg^(2+),its adsorption strength remains to be improved.